Process for providing a durable antistatic finish for synthetic textile materials



United States Patent Int. Cl. C08g 23/10 U.S. Cl. 260-2 6 Claims ABSTRACT OF THE DISCLOSURE Process for producing a resinous composition comprising reacting a polyamine with a halohydrin ether of a polyalkylene polyhydric alcohol to form a condensate with cyanuric halide; and the resinous product obtained. The resinous composition is useful as an antistatic agent for application to hydrophobic textile materials.

This is division of application Ser. No. 439,996 filed Mar. 15, 1965, and now U.S. Pat. No. 3,411,945.

This invention relates to a new, durable, antistatic finish for synthetic hydrophobic textile materials. More particularly, it relates to a new, durable antistatic finishing composition for hydrophobic textile materials, a method of applying the composition to such materials, the materials 80 treated, and a novel process for making the antistatic finish.

In general, textile fibers, yarns and fabrics made from synthetic hydrophobic materials, as for example the nylons, the acrylic fibers, the polyester fibers, acetate fibers and the like, become electrostatically charged whenever and wherever friction is applied to them. Therefore many disadvantages are encountered during mill processing and fabricating and more so during the end use of the materials manufactured. Aside from the discomfort to the individual wearing a garment which accumulates static electricity, there is also the serious problem of the attraction of dust and dirt particles which results in the garment having a soiled appearance. This usually causes frequent launderings or dry cleanings resulting in poor fabric life due to degradation caused by detergents and bleaches and the normal abrasion resulting from such processing.

The elimination of the static electricity in fabrics would ease the manufacturers problems, give more comfort to the consumer, and add greater life to the textile materials. It would also reduce hazardous conditions found in such places as operating rooms or in other places where ignition from static electricity could be dangerous.

Antistatic treatments of hydrophobic textile materials subject to the accumulation of static electricity are not new and have been employed by many in the past. However, many of these treatments have marked disadvantages; typical of these are the following: complicated methods of application, inability to be applied from aqueous media, instability with other chemicals, poor durability and soil-retentiveness of the finish applied when subjected to washing or dry cleaning, discoloration of the fabric, and loss of fabric strength or odor problems during pressing.

Typical commercially available antistatic agents exhibit wet-soil indices of 42, 27, and 20, for example, using untreated nylon fabric as a standard index of 1.0. High wet-soiling index is a major reason why many antistatic finishes, which are otherwise satisfactory, are not presently in common commercial use.

3,522,195 Patented July 28, 1970 In the ever increasing field of man-made fibers subject to the accumulation of static electricity, there is a genuine need for a good, durable antistatic treatment which when properly applied will not impart any important deleterious side effects upon the textile material finished therewith or cause discomfort to the consumer.

Accordingly, it is an object of the present invention to provide an antistatic finishing composition which, when applied to synthetic hydrophobic textile materials subject to the accumulation of static electricity, will impart thereto a durable antistatic finish.

A further object of the invention is to provide an antistatic finish capable of application in a conventional straightforward manner from an aqueous medium and which is compatible and stable with other textile agents and auxiliaries.

It is a still further object of the present invention to provide an antistatic finish which does not discolor fabrics finished therewith, does not reduce fabric strength, and does not result in odor problems during pressing or upon completion of finishing.

Another object of this invention is to provide an antistatic finish having a high degree of durability to washing and laundering, etc.

Another object is to provide an antistatic finish having a desirably low affinity for soil.

Other objects of this invention become apparent from the foregoing and following disclosure.

According to the present invention, I have found that a desired degree of durable antistatic properties may be imparted to hydrophobic textile material such as nylon, by applying thereto a polyalkylene glycol-polyamine resin at a pH in excess of about pH 7.5 followed by curing at a temperature of at least about 250 F. to about 350 F. I have further found that by reacting (l) a compound such as cyanuric chloride with (2) the polyalkylene glycol-polyamine resin, and applying (at any suitable pH) the product formed therefrom to the textile substrate, unexpectedly extended durability of antistatic properties are obtained, with or without subsequent conventional curing.

The term durable as employed herein simply relates to the durability of the finish provided by this invention to withstand ordinary washings or household launderings and dry cleaning, for example.

The term polyhydric alcohol includes the alcohols or glycols.

The term epihalohydrin includes the 1-halo-2,3- epoxypropanes.

This invention, as noted above, includes (1) a novel process of applying at a pH of at least about pH 7.5 a polyalkylene glycol-polyamine resin to the synthetic ma terial followed by curing at about 250 F. to 350 F., (2) a process and reactant product involving reacting a polyalkylene glycol polyamine resin with a cyanuric halide prior to the application of the reaction product to the synthetic material, to form a novel antistatic agent, (3) a novel process of applying the cyanuric halide reactant product to synthetic material, and (4) the antistatic synthetic fabrics formed by each of the above processes of applying the resins to synthetic materials.

The polyalkylene glycol-polyamine resin utilized in this invention is the reaction product of one or more halohydrin ethers reacted with one or more polyamines. Halohydrin ethers suitable as reactants include halohydrin ethers of polyalkylene polyhydric alcohols.

Halohydrin ethers with which this invention is concerned are generally prepared from polyalcohols by the use of an epihalohydrin, the process being well known. The preferred 'epihalohydrin is the chloro-compound epichlorohydrin. Other epihalohydrins are epibromohydrin and epiiodohydrin.

Condensation catalysts are used in reacting an epihalo hydrin with a polyalcohol for the formation of a polyhalohydrin ether. Typical catalysts are those of the Lewis acid type, including anhydrous AlCl ZnC1 SnCl and complexes such as the well-known BF etherates, etc., and the Bronstead acid type, including HF, H 50 and the like. Concentration of the catalysts may be varied from 0.1 percent to 2.0 percent depending upon the individual catalysts. A reaction temperature between about 70 C. and about 80 C. is recommended when boron trifiuoride etherate is used as the catalyst.

Suitable polyalcohols include the preferred polyethylene glycols with average molecular weights between about 200 and about 2,000, but molecular weights between about 500 and about 1,000 are preferred. Although it is preferred to use about 2 moles of epihalohydrin per mole of polyethylene glycol, between 1 mole and 3 moles may be used. If 2 moles of epihalohydrin are employed, the resulting halohydrin ether is a mixture of isomers, but the predominant product is believed to be of the typical structural formula shown below:

OH OH X-CHz-JJH-CHz-O-(-CHzCH2nO-(C%ICH-CH2X where X is a halide, and where n is an integer larger than zero.

Examples of other polyalcohols are: polypropylene glycols, and polytrimethylene glycols.

The polyamine reactant includes diamines, i.e., amines having two or more primary or secondary amino groups on separate carbon atoms, for example: trialkylene tetramine such as triethylene tetramine; ethylene diamine; propylene diamine; hexamethylene diamine; trimethylene diamine; tetramethylene diamine; tetraethylene pentamine; diethylene triamine; dipropylene triamine; etc.

The amines suitable for use in this invention are represented by the following typical formula:

H nmn-wmmh-iv-n where m and n each represent an integer larger than zero.

To form the polyalkylene glycol-polyamine antistatic resin, by reaction of halohydrin ether and amine, the reaction temperature may range from about 65 C. to about 135 C. The preferred temperature range, which gives an antistatic agent having superior antistatic prop erties, ranges from about 80 C. to about 100 C. Although it is not necessary-to employ a solvent for the reaction of halohydrin ether and amine, it is desirable to use a solvent such as alcohol, dioxane, and especially water.

In carrying out the reaction of the halohydrin ether and the polyamine, the polyamine is added to the halohydrin ether, and the exothermic reaction is controlled by the rate of addition. In the reaction of the amine with the polyhalohydrin ether, an amine-hydrohalide salt is formed. This amine salt is then desirably and subsequently reacted with an inorganic alkali to neutralize the hydrogen halide. Suitable alkalies are carbonates or bicarbonates of alkali metals, for example, sodium bicarbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, etc., and one equivalent, or less, of alkali per halohydrin group is generally used. Instead of adding alkali after the halohydrin ether and amine have reacted, a desirable method is to add alkali after about half of the halohydrin ether has been added to the amine. As the halohydrin ether and amine react, the product be comes quite viscous due to the formation of the aminehydrohalide salt. Since the halohydrin ether-amine condensate is less viscous than the amine-hydrohalide salt, the addition of alkali before the reaction is complete renders the mixture less viscous. The reaction can thus more readily be carried to completion. It is generally convenient to use dilute alkali, for example, a forty percent aqueous solution, the addition of alkali being continued 4 after the condensate is formed. Desirably, when all of the halohydrin has been added, about half of the alkali to be used has been added. Thus, the alkali can be added before or after completion of the reaction. Moreover, the alkali can be added at the start of the reaction (see Example 1).

The process described above is not the only process by'which applicants antistatic agent may be prepared. Applicants process for producing the antistatic agent of this invention does not require the utilization of a neutralizing alkali. However, as discussed above, it is advantageous to improve the antistatic properties of Applicants antistatic agent, to employ an acid-binding agent, such as sodium carbonate, potassium carbonate, sodium bicarbonate, etc. The acid binding agent preferably would be added in an aqueous solution, to accelerate the reaction.

Thus, the antistatic agent of this invention may be prepared either by the novel process which does not include alkali neutralization, or by a process which includes alkali neutralization.

Unexpectedly high durability of the antistatic finish, where cyanuric halide is not included as a reactant, is obtained by a novel process wherein the fabric treated with polyethylene glycol-polyamine resin is heated at a temperature of about 250 F. to about 350 F., preferably about 275 F., for from about 1 minute to normally about 3.5 minutes, employing normally therewith an acidbinding agent in an amount sufficient to establish an alkaline pH of at least about pH 7.5, i.e., not less than about pH 7.5.

In the preferred process for making the reaction product of a cyanuric halide with a polyalkylene glycol-polyamine to produce the preferred and novel antistatic resin of this invention, polyethylene glycol with average molecular weight of 600 is reacted with 2.2 moles of epichlorohydrin per mole of polyethylene glycol in the presence of a catalytic amount of boron trifluoride-etherate. The epichlorohydrin is added slowly to the mixture of polyethylene glycol and catalyst at a temperature between from about C. to about C., while cooling externally as required. To this reaction mixture, sodium carbonate is added and the mixture is boiled to destroy the catalyst and to remove trace amounts of volatile materials (by distillation, if desired). About 10% of triethylene tetramine, based on the weight of halohydrin ether present, is added slowly at a temperature between from about to about C. Glacial acetic acid is then added to give a pH of about 7. After the evolution of carbon dioxide ceases, a solution of about 10% of cyanuric chloride in dioxane is added slowly (about 30 minutes) at a temperature between from about 30 C. to about 35 C. After a further period of reaction (about 30 minutes), the viscous mixture is diluted with water to give an active ingredient content of 45-50%, and the pH is adjusted to about 4 with glacial acetic acid. The yield of active ingredient is considered to be theoretical. The original bright yellow color of this freshly prepared agent can be preserved by the addition of about 1% of sodium hydrosulfite based on the weight of active ingredients. The embodiment of this invention which includes a cyanuric halide as a reactant produces an antistatic agent which on textile material is durable for up to 40 or more launder ings of the type normally recommended for fabrics of synthetic hydrophobic fibers.

As discussed above, the applicant discovered that an antistatic agent of unexpectedly superior properties results when polyethylene glycol-polyamine described above is reacted with a cyanuric halide. It is not necessary that the polyethylene glycol-polyamine resin be isolated from its solution in which it was prepared, in order to react with the cyanuric halide. The amount of the cyanuric halide which may be employed normally ranges between from about 2% to about 40% based on the weight of the halohydrin ether-amine resin present. The antistatic agent having the preferred durability is formed by employing from about 8% to about 15% of the cyanuric halide. Although a cyanuric halide such as cyanuric chloride may be added as a solid, it is preferred that it be added as a solution in an inert, water-miscible solvent such as dioxane or acetone. The addition may be made at a temperature from about C. to about 50 C., preferably from about 25 C. to about 35 C. The reaction is continued at about the same temperature until about all of the halide atoms of the cyanuric halide have been replaced, as indicated by analysis for halide ion in the reaction mixture. The reaction mixture may then be diluted with water to the desired content of active ingredients.

It has been found that the antistatic agent having the superior antistatic durability properties is formed by employing cyanuric chloride as the preferred halide. However, it is within the scope of this invention to employ cyanuric fluoride or cyanuric bromide, for example.

For long storage stability, it is advisable to adjust the pH of the mixture to between about pH 2 and about pH 4, with an acid such as acetic acid. The storage stability, i.e., prevention of discoloration, of the finished composition may be enhanced by adding small amounts of reducing agents such as sodium hydrosulfite, as noted above.

The synthetic hydrophobic textile material which may be treated with the products of this invention include synthetic material such as nylon, acetate rayon, acrylic fibers, and terephthalic acid-ethylene glycol condensation products, for example. Any synthetic product which characteristically accumulates static electricity is the type of material on which the antistatic agent of this invention may be advantageously applied. The material may be in the form of woven or nonwoven goods, tufted and pile fabrics, knitted goods, felted goods and fibers both staple and filament. Applications can be made by padding, spraying, or any appropriate means. The finishes are conveniently applied from an aqueous bath.

Applications of the cyanuric halide reaction product may be made under acidic, neutral or alkaline conditions in a range between about pH 1 and about pH 11.0 The preferred pH range is between pH 3 and pH 10.

6 moles) of epichlorohydrin. The reaction mixture was maintained at a temperature of 75 C. for about 2.5 hours, adding 0.5 part of boron trifiuoride as a solution in about 1 part ether after the first 30 minutes.

To the mixture at about 5060 C. there were added about parts of water and 41.4 parts of sodium carbonate. After boiling the mixture for 10 minutes, 56.3 parts (0.385 mole) of triethylene tetramine were added over about 15 minutes at a temperature of 90-95 C. This temperature was maintained for about 30 minutes followed immediately by the addition of 50 parts of glacial acetic acid. The product solution or dispersion was adjusted to contain about 46% of active components.

' The above antistatic agent was applied to nylon tafleta at 1% solids O.W.F. from two aqueous pad baths of pH 7.0 and 8.5, respectively, the pH adjustments made by addition of sodium carbonate. The treated fabrics are referred to as A and B, respectively, in Table I. The fabrics were dried at 225 F. for 1.5 minutes and a portion of each fabric was then heated at 275 F. for 1 minute.

The yellowness index of the fabrics is calculated by the equation:

where R and R are reflectance values obtained on a recording spectrophotometer using a magnesium carbonate block as a reference standard at the wavelengths of 455 millimicrons and 577 millimicrons, respectively.

The antistatic activity is measured by the procedure based on Standard Test Method 761959 of the American Association of Textile Chemists and Colorists. Before the electrical resistivity of the fabric is measured, the fabrics are conditioned in the testing chamber at 70 F. and 30 relative humidity. Resistivity values below 500x10 ohms indicate good antistatic activities; resistivity values below x10 ohms indicate excellent antistatic activities.

The washes were carried out in a home-type automatic washing machine using a synthetic detergent and a washing cycle recommended for delicate fabrics.

TABLE I (ALKALINE pH) Antistatic Activity (ohms, X10

1 After 40 washes: warp 80x10", and fill 330x10.

Between about 0.25% and about 5.0% O.W.F., preferably between about 0.5% and about 2.0%, of the products of this invention are applied to the fabrics. The treated textile materials are normally dried by conventional methods, e.g., at about 225 F. for 1-2 minutes. If desired, the textile materials treated with the cyanuric halide reaction product can be heated at higher temperatures for short periods of time, but this is not required.

In order to illustrate the present invention, the following examples are given primarily by way of illustration. No specific details or enumerations contained therein should be construed as limitations on the present invention except insofar as they appear in the appended claims. All parts and percentages are by weight unless otherwise specifically designated.

EXAMPLE I To an anhydrous mixture of 450* parts (0.75 mole) of polyethylene glycol (average molecular weight 600) and 1.0 part of boron trifluon'de catalyst, introduced as a solution in about 2 parts of ether, at 7075 C. there were added over a period of about one hour 153 parts (1.65

Table I illustrates that the polyethylene glycolpolyamine, in which cyanuric halide is not a reactant, in the pad bath (1) in which a pH in excess of about pH 8 was employed and (2) in which the fabric treated thereby was subsequently heated to about 275 R, an antistatic finish of unexpectedly superior durability was obtained, as compared to the untreated fabric and as compared to the other fabrics treated with the finish at a lower pH and/ or without subsequent heating to 275 F. Also the table illustrates that the lack of or lessening of discoloration (yellowness) was highly desirable, being far below the index normally expected from the application of conventional finishes.

EXAMPLE II The antistatic finish of Example I was further reacted, as follows, after the addition of 50 parts of glacial acetic acid referred to in Example I.

When the evolution of carbon dioxide had ceased, the reaction mixture was cooled to between 30 and 35 C., and a solution of 59.2 parts (0.325 mole) of cyanuric chloride in parts of dioxane was added slowly at 30- 7 35 C. After an additional reaction period of 30 minutes, 100 parts of water were added, followed by about 30 parts glacial acetic acid to give a pH of 4.0 or lower. The product solution or dispersion contained about 46% of active component.

Two pad baths were prepared from the above antistatic agent. The pHs of the pad baths were adjusted to values of 7.0 for A and 8.5 for B by adding sodium carbonate. The baths were applied to nylon taffeta by a standard pad ding procedure. The fabrics contained 1% solids O.W.F. of the active component of the product. The treated fabrics were dried at 225 F. for 1.5 minutes and a portion of each fabric was heated at 275 F. for 1 minute.

The laundering operations were carried out in a homei type automatic washing machine using a synthetic detergent and using a washing cycle recommended for delicate fabrics.

The characteristics of the treated fabrics of Example II are illustrated in Table II.

TABLE IV (ACID pH 2.2)

Antistatic Activity (ohms, X10

Yellow- Initial washes ness Fabric Index Warp Fill Warp Fill Treated 7. 3 0. 2 0. 5 5. 7 12. 0 Untreated 1.6 50, 000 50, 000 50, 000 50, 000

Table IV illustrates that when the antistatic finish is the embodiment which includes reacting it with cyanuric halide (cyanuric chloride) and when it is applied at an acid pH followed by heating the treated fabric at about 350 F. for about 1 minute, the antistatic finish is un- TABLE II Antistatic Activity (ohms, X10

Yellow- Initial (40 washes) Heated ness Pad bath pH 275 F. Index Warp Fill Warp Fin Table II above, illustrates'that the antistatic finish produced by reacting polyethylene glycol-polyamine resin with cyanuric chloride exhibits superior antistatic activity at an alkaline pH. Subsequent heating at about 275 F, for example, does not have any detectable effect on the antistatic activity of the finish. Also the table illustrates that the degree of discoloration (yellowness) is highly desirable, being far below the index normally expected from the application of conventional finishes.

Comparison of the results shown in Table II with those of Table I demonstrate the superior antistatic properties of the product of Example II as compared with that of Example I.

EXAMPLE III TABLE III (ACID pH 2.2)

Antistatic Activity (ohms, X10

Yellow- Initial 40 washes ness Fabric Index Warp Fill Warp Fill Treated 7. 7 0. 1 3. 8 50, 000 50, 000 Untreated I. 6 50, 000 50, 000 50, 000 50, 000

Table III illustrates that when applied at an acid pH with the treated fabric heated at about 350 F. for about 1 minute, the antistatic finish (without having been reacted with cyanuric halide) fails to impart an antistatic activity of high duraibility.

EXAMPLE IV An aqueous pad bath was prepared containing the product of Example II. The pH of the bath was pH 2.2. The bath was applied to nylon taffeta by a standard padding procedure. The fabric contained 2% O.W.F. of the active component of the product of Example II, i.e., including expectedly high as compared with the control and has an unexpectedly high durability as well. The superiority of the finish is particularly apparent when the results are compared with those of Example III.

EXAMPLE V An aqueous pad bath (A) was prepared containing the product of Example I. The pH of the pad bath was adjusted to pH 9.5 with sodium hydroxide. The pad bath was applied to nylon taffeta by a standard padding procedure. The fabric contained 2% O.W.F. of the active ingredient of the product of Example I. The treated fabric was dried at 225 F. for a period of about one minute and was then heated at about 350 F. for about three minutes.

The antistatic activity was measured by the procedure of Example I.

The wet soiling characteristics of the treated fabric were measured as follows:

One gram of 22% aqueous colloidal graphite suspension was diluted with water to a volume of one liter. 4" x 4" pieces of treated fabric were placed in the graphite suspension contained in a 2-liter jar. The jar was shaken horizontally for 15 minutes, and the samples were rinsed with hot water at 80 F. and dried. The percent reflectance of the soiled fabric versus the unsoiled fabric was measured with a spectrophotometer.

The treated fabrics characteristics are illustrated in Table V.

TABLE V (ALKALINE pH 9.5)

Percent reflectance after soiling Warp Pad bath Table V illustrates that 1) when a finish which does not include the cyanuric halide reactant is applied at a pH of 9.5 followed by heating the treated fabric to about 350 for about 3 minutes, antistatic properties of unexpectedly high durability are imparted, and (2) as shown in the reflectance column, the treated fabric has highly desirable properties because of the low afiinity for soiling.

EXAMPLE VI Two aqueous pad baths (A and B) were prepared containing the product of Example II. The pH of the pad baths was adjusted to pH 9.5 for each bath, A by employing sodium hydroxide and B by employing sodiu'm carbonate. The baths were applied to nylon taffeta by a standard padding procedure. The fabrics contained 2% O.W.F. of the active ingredient of the product of Example II. The treated fabrics were dried at 225 F. for one minute and were then heated at 350 F. for three minutes.

The antistatic activity of the fabric was measured by the procedure of Example I.

The wet-soiling characteristics were determined by the procedure of Example V.

The treated fabric characteristics of Example VI are illustrated in Table VI.

TABLE VI Antistatic Activity (ohms, X

Percent Reflectance 40 washes after Pad bath soiling Warp F111 A (NaOH) 55 11 11 B (NazCOaL- 53 18 21 Untreated fab 65 50, 000 50, 000

EXAMPLE VII Three aqueous pad baths (A, B and C) were prepared containing the product of Example II. The pH of each of two pad baths (B and C) was adjusted by adding sodium carbonate. The baths were applied to nylon taffeta by a standard padding procedure. The fabrics contain 2% O.W.F. of the active component of the product of Example II. The treated fabrics were dried and then heated at 300 F. for 8 minutes.

The treated fabrics were tested for antistatic properties by allowing the fabric to remain for 4 hours in an atmosphere having 33% relative humidity. The fabrics were then rubbed with a wooden rod and held over an open dish containing finely divided carbon at a distance of about 1 /2 inches or lower. If the carbon was not attracted to the fabric, the fabric was considered to be antistatic.

The fabrics were repeatedly laundered in a home type automatic washing machine using a synthetic detergent and a washing cycle recommended for delicate fabrics. After the launderings, the antistatic tests were repeated. The launderings and antistatic tests were continued until the fabrics attracted the carbon particles and were, therefore, no longer considered to be antistatic.

The wet-soiling characteristics of the treated fabrics were measured according to the procedure described in Example V.

The treated fabric characteristics of Example VII are illustrated in Table VII.

TABLE VII (ACID pH) Amount of Pad Wet- N azCOa, Bath Soil Antistatic Pad bath percent pH Index Durability 0 2. 3 6. 5 20 washes. 10 5. 4 3. 9 At least 40 washes. 20 6. 7 1. 3 D0. 10 8. 1 Untreated 1. 0

EXAMPLE VIII Three aqueous padbaths (A, B and C) were prepared containing the product of Example II. The pH of two of the baths were adjusted to pH 7.0 (Bath B) and 9.5 (Bath C) by adding sodium carbonate. The baths were applied to a fabric of acrylic filament fibers by a standard padding procedure. The fabrics contained 2.5% O.W.F. of the active component of Example II. The fabrics were dried at 225 F. for 1.5 minutes, and then portions of the fabrics were heated at 330 F. for 2 minutes.

The antistatic activity was measured by the procedure of Example I.

The treated fabric characteristics of Example VIIII are illustrated in Table VIII.

TAB LE V III Fabric (over-all) antistatic activity (ohms, X10

Heated at 0 Pad bath pH 330 F. Initial washes 0. 21 88 0. 12 46 0. 20 36 3. 15 19 0. 16 60 C 3. 0 13 Untreated fabric. 50,000 50 000 The results shown in Table VIH demonstrated that applicants preferred antistatic agent, which is a reactant product of polyethylene glycol-polyamine resin reacted with cyanuric halide (cyanuric chloride), imparts a desirably high degree of initial antistatic activity at any one of a varying pH from acid to alkaline and irrespective as to whether the finish is subsequently heated to about 330 F.

It should be noted that in the preparation of applicants antistatic agent, the examples employed triethylene tetramine as the amine reactant, but that any other equivalent amine as discussed in the foregoing disclosure may be substituted therefor, such as tetraethylene pentamine, for example.

While the present invention has been demonstrated primarily by application to formed fabric, it will be appreciated that the antistatic finish may be applied to textile materials subject to the accumulation of static electricity, whether the material be a filament, fiber or a fabric, and whether the fabric be knitted, woven, felted or otherwise formed. Obviously, blends of the synthetic hydrophobic fibers with other filaments, such as cotton and the like which are not subject to the accumulation of static electricity, are contemplated since the composition of this invention has application to substrates which as a whole develop static electricity.

I claim:

1. A process for preparing a durable antistatic resin, said process comprising (1) reacting a polyamine selected from the group consisting of alkylene polyamines and 1 l polyalkylene polyamines, with a halohydrin ether of a polyalkylene polyhydric alcohol, thereby forming a condensate, and (2) reacting said condensate with a cyanuric halide.

2. A process according to claim 1, in which said polyalkylene polyhydric alcohol is a polyethylene glycol.

3. A process according to claim 2, in which said cyanuric halide is cyanuric chloride.

4. A durable antistatic resin comprising a halohydrin ether of polyethylene glycol-polyamine resin reacted with from about 2 to percent, based on the weight of said resin, of cyanuric chloride, said polyarnine being selected from the group consisting of alkylene polyarnines and polyalkylene polyamines.

5. A process according to claim 4, in which said poly- 15 alkylene glycol is a polyethylene glycol and in which said trialkylene tetramine is triethylene tetramine.

6. A process for preparing polyalkylene glycol-polyamine antistatic resin consisting essentially of (A) Reacting (1) a polyalkylene glycol with (2) epichlorohydrin at from about C. to about C. in the presence of a condensation catalyst, sufiiciently to form a halohydrin ether reaction product; and

(B) Reacting (1) said halohydrin ether with (2) about 10% of trialkylene tetramine, based on the weight of said halohydn'n ether, while maintaining the mixture temperature at from about C. to about C., sufiiciently to form a reaction product, adding glacial acetic acid to neutralize said reaction product; and

(C) Reacting (1) said reaction product with (2) from about 8% to about 40% of cyanuric chloride, based on the Weight of said reaction product, and

(D) Adding glacial acetic acid to said cyanuric chlon'de reaction product, in an amount sufiicient to give a pH of between from about pH 2 to about pH 4.

10/ 1963 Wohnsiedler et a1. 10/ 1963 Frotsoher.

WILLIAM H. SHORT, Primary Examiner 20 T. PERTILLA, Assistant Examiner U.S. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Dated July 28 1970 Patent No.

Tsai Hsiang Chao Inventor(s) rs in the above-identified patent It is certified that error appea by corrected as shown below:

and that said Letters Patent are here OH OH v 1 Col. 10, line 32, delete "VIIII" and insert VIII Signed and sealed this 16th day of May 1972.

(SEAL) A t; he s t:

EDWARD I'LFLETCHER ,JR. ROBERT GOTTSCHALK Attesting Officer- Commissioner of Patents USCOMNPDC SOSIB-PBQ e us. covnuuim unmno OFFICE: u" 0-in-3 FORM PO-IOSO (10-69) 

